Treating cellulose derivative materials



- such as knitting and the like.

Patented June 10, 1941 TREATING CELLIJLOSE DERIVATIVE MATERIALS JosephB. Dickey and James B. Normington, Rochester, N. Y., assignors toEastman Kodak Company, Rochester, N. Y., a corporation of New Jersey NoDrawing. Application December 2, 1938, Serial No. 247,095

7Claims.

This invention relates to the conditioning of textile yarns and moreparticularly to the conorganic derivatives of cellulose such ascellulose acetate, cellulose propionate, cellulose acetate propionate,and cellulose acetate butyrate, to render them more amenable to textileoperations This invention also relates to compositions of matter inwhich cellulose derivatives such as cellulose acetate, cellulose nitrateor cellulose ethers, are combined or mixed with other substances, suchas a compatible plasticizer, anda common solvent for 'both, with orwithout other useful addition agents, so that the resulting product willhave properties such as will make the composition highly advantageousfor use in the plastic and analogous arts, such for instance, as themanufacture of wrapping sheets, photographic film, artificial silk,varnishes or lacquers, and the like.

As is well known in the manufacture of yarns, particularly thosecomposed of or containing cellulose organic derivatives, it is necessaryto treat the yarn in order to reduce the tendency toward breakage of theindividual filaments or fibers when they are subjected to variousmechanical strains and to lubricate the yarn in order to facilitatehandling in such operations as spinning, twisting, winding and reeling.It is also necessary to treat yarn to adapt it for use as warp orfilling or for the manufacture of vari ous types of knitted fabrics. Inknitting, it is particularly important that the yarn be soft and pliablein order that it may conform readily to the contour of the needles andthus produce a closely knit fabric free from such defects as stitchdistortion, pin holes, laddering, and the like.

Heretofore it has been proposed to employ softening agents such aspolyhydric alcohols and similar agents as ingredients of yarnconditioning or lubricating formulas, generally inconnection withmineral, animal or vegetable oils. It has been found, however, that mostof the known softening agents and the various formulas containing themhave certain drawbacks, one of the most serious of which is high vaporpressure, and in some cases too drastic a solvent action on the yarn.Many of such agents possess slight or insuflicient solvent power for thelubricants with.

which they are used, and it is accordingly necessary to employ blendingagents or emulsifying agents in order to obtain'operable yarn treatingformulas. In addition, many of the known softening and lubricatingagents are insufilciently solublein water to permit satisfactory removalby aqueous scour baths.

While in the plastic and related arts cellulose acetates,' nitrates andethers have been known for decades, it has also been known that toutilize them it is necessary to, mix therewith such plasticizing orconditioning agents as camphor, castor oil, triphenyl phosphate,monochlornaphthalene or the like. Certain of these and other additionagents are also added for the purpose of reducing the inflammability ofthe product. Plastic inducing agents, such as the higher alcohols andtheir esters, are sometimes also added. Similarly, addition compounds ofvarious kinds have been employed to increase flexibility, transparency,toughness, and other properties which will enhance the value of tileresulting product. Addition products for the same or similar purposesare also added to cellulose acetates, nitrates and ethers to preparethem for use in the other plastic arts, such as in the manufacture oflacquers, varnishes, artificial silk filaments, moulded compounds andthe like. While the plasticizers or other addition agents heretoforediscovered have had their utility in the art, the increasing use towhich cellulose derivatives have been put and the increasing number ofdesirable properties required of the cellulose derivative for mostpurposes has made the discovery of new and economical plasticizers orother addition agents a matter of considerable importance to the art.

This invention has as its principal object to provide an entirely newclass of yarn conditioning agents which are particularly adapted for thetreatment of yarns composed of or containing organic derivatives ofcellulose and capable of lubricating, softening and rendering such yarnsmore amenable to knitting and other textile operations. A further andspecific object is to provide a class of conditioning agents whichaugment or assist the lubricating action of various lubricants whenapplied to such yarns. A

. still further object is to provide yarn softening and lubricatingformulas which can be readily removed from the yarns by the usual scourbaths. A still further object is to provide an improved method fortheconditioning of yarns, particularly those composed of or containingorganic derivatives of cellulose such as cellulose acetate, whereby theyarn isrendered soft and pliable and capable of employment in a varietyof textile operations where complicated designs 01' stitches areemployed. Another object is to provide an improved type of yarn which isespecially amenable to textile operations including circular knitting,weaving, spinning and the like. Still another object of this inventionis to produce a composition of matter which may be made into permanentlytransparent, strong and flexible sheets or films of desired thinnesswhich are substantially waterproof, are unaffected by ordinaryphotographic fluids and possess the desired properties of a support forsensitive photographic coatings. Yet another object of our invention isto produce a composition which is capable of easy and convenientmanipulation in the plastic and analogous arts, such as in themanufacture of sheets, films, artificial silk filaments, varnishes,lacquers and the like, and to produce a composition which will notinjure, or be injured by, the substances or surfaces with which it isassociated during manufacture. Other objects will appear hereinafter.

These objects are accomplished by the following invention which, in itsbroader aspects, comprises the discovery that acetals and hemi acetalsof chloral and their derivatives, the preparation of which is referredto in J. Ind. Chem. Soc. 13, 118 (1936), may be used as yarnconditioning agents and particularly as softening agents, with orwithout the addition of animal, mineral, or vegetable oils, in thetreatment of yarns composed of or containing organic derivatives ofcellulose. In addition to the compounds referred to in this article wemay prepare the propionate, butyrate, valerate etc. methoxy acetate,benzoate, furoate, tetrahydrofuroate, etc. We have found that thesecompounds when employed as described in the detailed examples set forthbelow have a slight solvent and/or softening action on cellulose organicderivative yarns which renders such yarns soft and pliable without atthe same time having too drastic an action thereon. These acetal andhemi-acetal compounds have, respectively, the following generalformulas:

wherein X is a substituent selected from the group consisting ofhydrogen and acyl, and R is a radical selected from the group consistingof alkyl and hydroxy alkyl groups.

In the lubrication of textile filaments, particularly those composed ofcellulose-acetate, dif-' ficulties have been encountered where the usualagents for lubrication have been used such as mineral oils and blown andunblown drying and semi drying oils such as sperm, neats-foot, olive,teaseed, soya bean, peanut etc., or any combination of the above. Wehave found that chloral derivatives of the type described in the articlelisted above, when used in conjunction with the lubricants listed above,give improved results in various textile operations such as knitting,weavacetate and may be used alone or in conjunction with other materialsin the production of threads, films, lacquers, molded products, etc.,composed of these materials.

Our invention also comprises the discovery that valuable properties maybe induced in and/or contributed to compositions containing cellulosederivatives such as cellulose acetate, by adding thereto as plasticizingcompounds the above mentioned compounds. This class of compounds iscompatible with cellulose derivatives and particularly compatible withcellulose acetate in the percentages .hereinafter given.

TREATMENT or TEXTILE YARNS In accordance with the invention thesecompounds may be applied directly to the yarn during or after spinning,or may be added to the spinning solution itself. We have found thatthese compounds have exceptional solvent powers which enable them todissolve mineral oils and blown and unblown, drying and semi-dryingvegetable and animal oils and accordingly they may be, and preferablyare, employed as ingredients of yarn conditioning or lubricatingformulas in conjunction with agents which function wholly or partiallyas lubricants.

In the following examples and description we have set forth several ofthe preferred embodiments of our invention, but they are included merelyfor purposes of illustration and not as a limitation thereof.

Our invention will be more readily understood by reference to thefollowing examples in which typical applications of the invention areset forth.

Example 1 A compound having the formula:

CH:OH no-o-on-con moon-col,

(glycol bis-chloralhemiacetal) is applied to textile materials (silk,cotton, wool, cellulose acetate, viscose, etc.) by means of a bath,wick, roller, spray, etc. to facilitate their knitting, weaving,spinning and the like. If the yarn is intended primarily for knitting,the amount of conditioning liquid applied may vary from 425% by weightof the yarn. If the yarn is intended ganic derivatives of celluloseincluding cellulose primarily for weaving, the amount of conditioningliquid applied may vary between 1-5% by weight of the yarn.

Example 2 Percent CHr-OH HOH Glycerol chloral H 20 I H!-C C1: H Oliveoil and applied to textile materials such as silk, wool, celluloseacetate, viscose, etc., as described in Example 1. If the yarn isintended primarily for knitting, the amount of'conditioning liquidapplied may vary from 425% by weight of the yarn, and if the yarn isintended for weaving, the amount of liquid applied may vary between 15%by weight of theyarn. Cellulose acetate filaments or fibers treated asdescribed above are quite soft and pliable and give improved results ofyarns, particularly? those composed of or containing cellulose acetate,cellulose acetate propionate, cellulose acetate butyrate, andsimilarcellulose organic acid esters in accordance with our invention and whichrender such yarns soft and pliable and especially well adapted forvarious textile operations, particularly knitting, are as follows:

Example 3 Parts C0]: OC:H OCCHr 2] r 0 OCCH:

(B-acetoxyethylchlcral hemiacetal acetate) Blown olive 80 Example 4 H0-011: ChC-C [2O 0-CH), Light mineral oil 80 Example 5 CH:OCCSH1CHz-Ofi-CIHT 0 u 30 H Hr-0C Ch Blown sperm oil .I. 70

Example 6 4o CHrCHa cm-o-c-tm Ha I mm 3o 0 H CC-Cla Hg-O (Glycerolchloralacetal-tetrahydrolnroate). I Blown neats-ioot oil 70 Example 7 CHo-cn-c on 20 0 Hz-O CHr-C C1: (Ethylene glycol bischloral hemiacetalether) Blown 30 Salt of sulionated olive oil -Q. 20 White mineral ll 10Oleic MM 12 Ethan lamin Wateri- 7 60 Example 8 011,-0 c-cm on-oo-cn. H:i

c-c Cl: ii (Diacetin chloral hemlacetal) s 11.. co 1.23 31? 20 Example 9Parts 0 C 0 C H:

CHr-O- C C]: i

H HzOOC Ch 0 O CH:

(Ethylene glycol bischloral hemiacetal diacetate) Tetrahydroiuriurylformal 20 Blown soya bean oil 20 Example 10 A 20% solution of celluloseacetate in acetone, in which is incorporated 1-25% by weight or CHI-0c-c Cl: H 11,-0 (2-trichloromethyldioxalane 1,3) is extruded throughfine orifices into an evaporative atmosphere. The filaments thusproduced are wound or twisted and wound. Yarns produced from filamentsthus prepared are pliable and suitable for knitting.

Any of the above compositions may be applied to the yarn intended foruse in circular knitting by means of a bath, wick, spray, roller, pad orany suitable means. The amount of conditioning liquid applied may varybetween 5-25% by weight of the-yarn. Usually, however, the amount ofconditioning liquid applied is about 10-15% by weightof the yarn. Yarncomposed of cellulose acetate conditioned as described above givesexcellent results when used in the circular knitting process.

As will be apparent from the above examples and description theconditioning agents of our invention may be applied by a wide variety ofmethods. For example, we may employ the agent as an ingredient of thespining dope from which the filaments are formed, the amount of theagent so employed depending upon a number of factors, such as theparticular cellulose derivative used in making the yarn, the solvent orsolvent combination used in making up the spinning solution, and thedegree of softness or pliability desired in the yarn, etc.

If the conditioning agent is to be applied to the yarn after spinning,this may be done by bringing the yarn in contact with a wick, roll, orfelt wet therewith, or the liquid may be applied by immersion, spray, orotherwise. The particular point at which the liquid is applied may vary.It may, ior example, be applied to the yarn inside or outside thespinning cabinet,, between the guide and godet roll, between thegodet orother roll or guide and the point of winding and/or twisting. In somecases, the liquid may even be applied to the yarn after winding ontocones, spools, bobbins, or the e or by the ,so-called bobbin. to bobbin?method. ,In the case of i staple fiber manufacure, the liquid may beapplied to the yarn prior to, or after cutting into staple lengths.

The amount of the agent so employed will vary widely depending upon theresults desired, the specific nature of the material to which the 5agent is applied, the use to which the yarn is eventually to be put andother factors. For example, in a given case where a cellulose organicacid ester yarn such as a yarn composed of cellulose acetate, isintended for knitting, about 4 to 25% or more by weight, based on theweight of the dry yarn, may be satisfactory, while if the yarn isintended for weaving, the amount may vary between about 1 and 5%.

Although in the above examples we have referred primarily to yarntreating compositions containing only the conditioning agent and an oil,other ingredients such as solvents, non-solvents, emulsifying agents,blending agents and the like, may be added within the scope of ourinvention. Likewise, various dyes or other coloring matter may beincluded in case it is desired to permanently or fugitively tint or dyethe material undergoing treatment.

Although we have found it convenient to illustrate our invention byreference to compositions containing specific percentages of the variousingredients, these percentages may vary widely depending upon theparticular purpose for which the composition is intended. For example,if it is desired to control the solvent or softening action of theconditioning agent, the amount of the agent may be adjusted as, forexample, by reducing the amount of the agent and correspondinglyincreasing the amount of oil or other ingredient.

While we have described our invention with particular reference to thetreatment of yarns composed of organic derivatives of cellulose such* ascellulose acetate, the conditioning agents and formulas described hereinare applicable to the conditioning of many other types of cellulosederivative yarns such as those composed of or containing cellulosepropionate, cellulose butyrate, cellulose acetate propionate, celluloseacetate butyrate, ethyl cellulose, methyl cellulose, benzyl celluloseand others, as well as to the conditioning of silk, wool, cotton,viscose and other natural or artificial materials.

The term yarn as used herein and in the claims is to be understood asincluding a single filament, a plurality of filaments associated intothe form of a thread, either of high or low twist, single or multiplethreads associated or twisted together, composite threads composed of amixture of natural and artificial filaments or a composite thread formedby twisting together individual strands of natural or artificialmaterials, as well as cut staple fibers produced from natural and/orartificial filaments or threads and spun yarn produced from such staplefibers.

As indicated above, the yarn conditioning agents of our invention areexceptionally good solvents for a wide variety of mineral, blown andunblown, drying and semi-drying animal and vegetable oils such ascottonseed, olive, castor, 5 neats-foot, sperm, and other oils. Thisenables them to be used with any of such oils in making up a variety ofyarn treating formulas of varying composition.

The yarn conditioning method and compositions of our invention possessmany outstanding advantages. The fundamental and outstandingcharacteristic of the agents employed in accordance with the inventionis their ability to soften ya pecially those composed of or containingorganic derivatives of cellulose such as cellulose acetate and renderthem soft and pliable and amenable to various textile operations,especially operations such as those involved in weaving and knittingwhere complicated designs or stitches are employed, without too drastican action on the yarn material. Another outstanding characteristic ofthese compounds is their exceptional solvent power for a wide variety ofmineral, animal, and vegetable oils and their ability to act aslubricating assistants in conjunction with these oils when applied tosuch yarns. In addition, due to their solubility in water, they may bereadily removed from yarns and fabrics by means of the usual aqueousscour baths. By employing the yarn conditioning agents and method of ourinvention as herein described, one is enabled to obtain highlysatisfactory'results in the manufacture of yarns and woven fabrics andespecially the production from these yarns of closely knit fabrics freefrom defects such as pin holes, stitch distortion, laddering and thelike.

Use: or COMPOUNDS AS Pmsrrcrzaas The following examples illustratepreferred compounds in which the above mentioned compounds are employedin accordance with our invention.

A cellulose acetate proprionate lacquer is prepared as-follows:

Parts Cellulose acetate propionate (acetone soluble) 5 CHPO C-C HGlycerol chloral acetate HOCOCH;

H 0 0-0 Cl:

dissolved in parts of a solvent composed of- Amtnno 60 B-methoxyethanol3O Benzene 10 Example 14 Films or foils composed of cellulose acetatecan be prepared from the dope:

Parts Cellulose acetate (acetone soluble) 100 C H:O\

0-0 G]; i 50 H Hz-O (Z-trichloromethyl (lloxolane-l, 3)

Acetone or methyl ethyl ketone 500 Typical plastic compositionscontaining the derivatives of chloral are illustrated as follows:

Example 15 Parts Cellulose nitrate 100 t 60 CHz-OCHC Cl:

(Ethylene glycol bischloml hemiacetal ether) Pigment Example 16 PartsCellulose butyrnin 100 GOO-CH:

om-ocn-ccu coo-cm 1o (i7H0-CHCCh CH: (Propylene glycol-bischloralhermiawtal diacctate) 10 Example 17 Ethyl cellul 100 o-clne-ocrachcc-ocml-oon.

(Chloral dimethoxy ethyl acetal) Example 18 Methyl methacrylic resin 100CH1CH1 20 CHz-0C-CH CH2 0 CHr-CH: m t h d I to Glycerol chloral te ra yto uroa CH OC CH CHI O H CHz-OC-CG];

H Example 19 Cellulose acetate I 100 OKs-0H (SHOE):

H Hg-O-C-CC]: 36.) Mannitoldichloral- H 30 H OH-0-CC o1:

300 Acetone. Methyl L 100 Compositions of matter prepared as'abovedescribed may be deposited upon any suitable filmforming surface to forma film or sheet, as is well known to those skilled in the art. A film soproduced has permanently brilliant transparency and low inflammability,burning no more readily than ordinary newsprint. Such film is exceedingly tough and flexible, as shown bythe fact that it will withstandmany folds upon a modifled Schopper fold-tester (commonly used for suchpurposes) without breaking and that even after being subjected for aconsiderable number of days to air maintained at a temperature of 65 C.the fllm still maintains flexibility (in contrast to almost completelack of flexibility where no plasticizer is used) demonstrating that thefilm will withstand ordinary usage satisfactorily for many years. Thesum total of the above advantageous properties of a product producedfrom our new composition is considerably in excess of that of productsproduced with what have previously been regarded as the betterplasticizers.

In order that those skilled in this art may better understand ourinvention we would state, by way of illustration, that for themanufacture of photographic fllm or other sheets ournew composition ofmatter may in general be compounded as follows: 100 parts of acetonesoluble cellulose acetate, i. e. cellulose acetate containing from 38%to 42% acetyl radical, approximately, is dissolved with stirring atatmospheric temperature in 300 to 500 parts, preferably 400 75 parts, byweight, of acetone. To this solution may be added from 5-50 parts byweight, of any one of the above plasticizers, it being found preferableto employ approximately 30 to 40 parts thereof. The amount ofplasticizer may be decreased or increased, depending upon whether it isdesired to decrease or increase, respectively, the properties which thisplasticizer contributes to the finished product.. The amount of solventemployed may also be decreased or increased, de-

pending upon whether it is desired to have a more or less freely flowingcomposition, respectively. I

Other similar solvents than those mentioned above which are compatiblewith the cellulose acetate and our new plasticizers may also occur tothose skilled in this art. In like manner our plasticizers may becompounded with other single or mixed organic esters of cellulose, suchas cellulose aceto-stearate, aceto-malate, or cellulose nitro-acetate,or with the cellulose ethers, a suitable solvent which will dissolveboth' the cellulosic derivative and the plasticizer being employed.

Our novel plasticizers may be employed also with advantage in connectionwith a number of the knownlacquer and varnish formulas with which it maybe found to be compatible. In such cases the plasticizer is usuallyfirst put into solution with the cellulose derivative solution and, ifnon-solvents are added, only to such an extent as will not precipitatethe derivative from solution. Also the plasticizer is usually employedin larger amounts, such as from 50 to 60 parts, in compounding lacquers.Other uses within thescope of our-invention will also suggest themselvesto those skilled in the art and are to be included within the scope ofthe claims appended hereto.

What we claim is:

1. The process of conditioning yarn to render it more amenable totextile operations including knitting, weaving, spinning and the likewhich comprises applying thereto a lubricating and softening compositioncontaining as its essential lubricating and softening component anacetal derivative of chloral selected from the group consisting of theacetals and hemi-acetal having the following general formulas:

wherein X is a substituent selected from the group consisting ofhydrogen and acyl, and R is a radical selected from the group consistingof alkyl and hydroxy alkyl groups.

2. The process of conditioning yam composed of or containing organicderivatives of cellulose to render it-more amenable to textileoperations including knitting, weaving, spinning and the like whichcomprises applying thereto a lubricating and softening compositioncontaining as its essential lubricating and softening component anacetal derivative of chloral selected from the group consisting of theacetals andhemi-acetals having the following general formulas:

wherein X is a substituent selected from the group consisting ofhydrogen and acyl, and R is a radical selected from the group consistingof alkyl and hydroxy alkyl groups.

3. The process of conditioning yarn composed of or containing celluloseacetate to render it more amenable to textile operations includingknitting, weaving, spinning and the like, which comprises applyingthereto a lubricating and softening composition containing as itsessential lubricating and softening component an acetal derivative ofchloral selected from the group consisting of the acetals andhemi-acetals having the following general formulas:

R and ChC-C-OR wherein X is a substituent selected from the groupconsisting of hydrogen and acyl, and R is a radical selected from thegroup consisting of alkyl and hydroxy alkyl groups, and a. textilelubricant.

5. Textile yarns amenable to textile operations including knitting,weaving, spinning, and the like, impregnated with a lubricant containingas its essential lubricating and softening component an acetalderivative of chloral selected from the ClaCC group consisting of. theacetals and hemi-acetals having the following general formulas:

wherein X is a substituent selected from the group consisting ofhydrogen and acyl, and R is a radical selected from the group consistingof alkyl and hydroxy alkyl groups.

6. Textile yarns composed of or containing organic derivatives ofcellulose amenable to textile operations including knitting, weaving,spinning and the like, impregnated with a conditioning agent comprisingan acetal derivative of chloral selected from the group consisting ofthe acetals and hemi-acetals having the following general formulas:

R and ClzC-C-OR wherein X is a substituent selected from the groupconsisting of hydrogen and acyl, and R is a radical selected from thegroup consisting of alkyl and hydroxy alkyl groups.

7. Textile yarns composed of or containing organic derivatives ofcellulose amenable to textile operations including knitting, weaving,spinning, and the like, impregnated with a conditioning agent comprisingan acetal derivative of chloral selected from the group consisting ofthe acetals and hemi-acetals having the following general formulas: I

ClaC-C wherein X is a substituent selected from the group consisting ofhydrogen and acyl, and R is a radical selected from the group consistingof alkyl and hydroxy alkyl groups, and a textile lubricant.

ClzC-C JOSEPH B. DICKEY. JAMES B. NORMINGTON.

CERTIFICATE OF CORRECTION.-

Patent No. 2,215,260. 1 June 10, 19M.

JOSEPH B. DICKEY, ET AL.

It. is hereby certified that error above numbered patent requiringcorrec ed specification, line 8,

appears in the printed specificationof the tion as followe;

I theheading to the printforeign filing date, for "December 2, 1958"read -December 21, l958-; page 5, first eolumn, after the formula andbefore "Blown sperm oil --70" Dibutyrinchloralhemiacetal butyrate)--Exam le 5,

Henry Van Arsdale, (Seal) Acting Commissioner of Patents.

